Determination of trace rare earth elements by inductively coupled plasma optical emission spectrometry after preconcentration with immobilized nanometer titanium dioxide

A simple and sensitive method is presented for the determination of dopamine with a nanoscale ceria ion-selective CMC (carboxymethyl cellulose) membrane electrode by means of the Belousov–Zhabotinsky oscillating chemical reaction. The electrode exhibits excellent potential response. If the concentration of dopamine is in the range of 4.9 × 10⁻⁵ to 2.4 × 10⁻⁷ mol · L⁻¹, the change in oscillating amplitude is proportional to the concentration of dopamine, with a correlation coefficient of 0.9987 and a standard deviation of 0.17%. A recovery of 97.5–105.0% was obtained. Interference was also studied. The use of a nanoscale ceria ion-selective membrane-working electrode improved the sensitivity of the determination method.     

Enantiomeric resolution of persistent compounds of technical toxaphene (CTTs) on t-butyldimethylsilylated β-cyclodextrin phases

Summary Eight of the most important single compounds of technical toxaphene were separated on t-butyldimethylsilylated β-cyclodextrin (β-BSCD) diluted in a medium polar phase using gas chromatography with electron capture detectors (GC-ECD). The enantiomeric resolution of all compounds was obtained in one GC run. The β-BSCD phase also separated the enantiomers of oxychlordane, cis- and trans-chlordane as well as α-HCH. Problems in the enantioselective determination of CTTs in biological samples are discussed. Finally, the enantioselective determination of the two most recalcitrant CTTs in biological samples was achieved using electron capture negative ionization mass spectrometry (GC-ECNI-MS) in the single ion monitoring (SIM) mode. Presented at the 21^st ISC held in Stutgart, Germany, 15^th–20^th September, 1996.     

Determination of biogenic amines in fermented beverages and vinegars by pre-column derivatization withpara-nitrobenzyloxycarbonyl chloride (PNZ-Cl) and reversed-phase LC

Summary The reagentp-nitrobenzyloxycarbonyl chloride (PNZ-CI) was used for pre-column derivatization of biogenic amines (BAs) at ambient temperature followed by reversed-phase, liquid-chromatographic separation of the derivatives. Optimized derivatization of samples was achieved within 10 min in borate buffer by adding PNZ-Cl in acetonitrile (MeCN). Excess reagent was scavenged by subsequent addition of glycine in water. For LC a Superspher^? RP-18e column and gradient elution using a ternary gradient system containing sodium acetabe buffer (pH 6.1), sodium acetate buffer (pH 4.3) and MeCN, were used. The PNZ-derivatives were quantified by their UV-absorption at 265 nm. Detection limits of BAs were approximately 62–1000 μg L⁻¹ (injected amounts: 53–850 pg) at a signal-to-noise ratio of 3:1. The coefficients of determination were 0.9906–0.9992. Diaminohexane was used as internal standard. Recoveries of BAs ranged from 78–93% depending on the food matrix. This method was applied to the quantitative determination of 2-phenylethylamine, tryptamine, serotonin, putrescine, histamine, cadaverine, tyramine, spermidine, and spermine, in beer, wine, vinegars, and lactic fermented cabbage juice. Parts of the results were presented at the 35th Congress of the “Deutsche Gesellschaft für Ern?hrung”, Kiel, 19^th–20^th March 1998, and the “Regionaltagung der Lebensmittelchemiker”, Giessen, 9^th–10^th March 1998     

Analysis of halogenated methoxybenzenes and hexachlorobenzene (HCB) in the picogram m−3 range in marine air

Summary Halogenated methoxybenzenes (halogenated anisoles) and hexachlorobenzene (HCB) have been analyzed in marine air samples from the lower troposphere of the East Atlantic Ocean, taken on the German, research vessel ‘Polarstern’ during two cruises in 1993 and 1994, and in air samples from the North Pacific Ocean (1995). The high-volume sampling method, sample preparation and analysis by HRGC-ECD and HRGC-MSD-SIM are described. The effectiveness of a new graphitized-carboncovered silica sorbent (ANGI-Sorb B) for the sampling of semi-volatiles is demonstrated. Eight congeners of the halogenated anisoles and HCB were detected in almost all marine air samples. The concentrations of the chloroanisoles, which show a distinct north-south interhemispherical gradient, were between 0.2 and 145 pg m⁻³; for the bromaanisoles concentrations were between 0.2 and 42 pg m⁻³. Only a weak inter-hemispheric gradient was observed for HCB at levels of 10–40 pg m⁻³. Levels of HCB were approximately 100 pg m⁻³ in continentally influenced air. Biogenic and indirect anthropogenic sources of the halogenated anisoles are discussed. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Experimental evidence for the formation of doubly charged oxide and hydroxide ions in inductively coupled plasma mass spectrometry

The formation of doubly charged polyatomic ions in inductively coupled plasma mass spectrometers was investigated using commercially available instruments. The species observed were ThO²⁺ and ThOH²⁺, which were found in similar amounts with the different instruments used in this study, when operated under routine analytical conditions. The signal ratios for ThO²⁺ were between 1.8 × 10^–4 and 4.2 × 10^–4 relative to the singly charged elemental ion and between 1.4 × 10^–2 and 2.2 × 10^–2 relative to the doubly charged elemental ion. The formation of ThOH²⁺ was between 1.1 × 10^–4 and 2.8 × 10^–4 relative to the singly charged elemental ion and between 0.72 × 10^–2 and 1.3 × 10^–2 relative to the doubly charged elemental ion. A mechanism is proposed for the formation of the doubly charged oxide and hydroxide ions that is based on the condensation of the doubly charged elemental ion with water or oxygen molecules in the interface region of the mass spectrometer. Received: 20 December 2000 / Revised: 19 March 2001 / Accepted: 22 March 2001     

41Ca ultratrace determination with isotopic selectivity > 1012 by diode-laser-based RIMS

⁴¹Ca ultratrace determination by diode-laser-based resonance ionization mass spectrometry with extremely high isotopic selectivity is presented. Application to environmental dosimetry of nuclear reactor components, to cosmochemical investigations of production cross sections, and biomedical isotope-tracer studies of human calcium kinetics are discussed. Future investigations are possible use in ⁴¹Ca-radiodating. Depending on the application, ⁴¹Ca isotopic abundances in the range of 10^–9 to 10^–15 relative to the dominant stable isotope ⁴⁰Ca must be determined. Either double- or triple-resonance optical excitation with narrow-band extended cavity diode lasers and subsequent non-resonant photoionization of calcium in a collimated atomic beam were used. The resulting photoions are detected with a quadrupole mass spectrometer optimized for background reduction and neighboring mass suppression. Applying the full triple-resonance scheme provides a selectivity of ∼ 5 × 10¹² in the suppression of neighboring isotopes and > 10⁸ for isobars, together with an overall detection efficiency of ∼ 5 × 10^–5. Measurements on a variety of sample types are discussed; the accuracy and reproducibility of the resulting ⁴¹Ca/⁴⁰Ca isotope ratios was better than 5%. Received: 4 January 2001 / Revised: 19 February 2001 / Accepted: 27 February 2001     

Fast determination of gold in large mass samples of gold ores by photoexcitation reactions using 10 MeV bremsstrahlung

The determination of gold is based on the photoexcitation reaction ¹⁹⁷Au(γ,γ’)^197mAu with the half-life of 7.73 seconds and energy of emitted gamma-rays of 279 keV. Three 100 ml aliquots of coarsely ground Au-ore (grains <2 mm) corresponding to ca. 150–180 g were irradiated for 20 seconds with bremsstrahlung of maximum energy 10 MeV produced by a microtron at the electron beam current of 30–40 μA, 1–10 times reactivation was applied. After 3 seconds of decay, samples were measured for 20 seconds using scintillation or semiconductor gamma-spectrometry with the detection limits for an ideal sample down to 0.5 μg·g⁻¹ and 0.1–0.2 μg·g⁻¹ of Au, respectively. Content of U and Th undergoing photo-fission increases the detection limits several times.     

Multiresidue pesticide analysis of fruits by ultra-performance liquid chromatography tandem mass spectrometry

Ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC–MS–MS) has been used for screening and quantification of 32 pesticides and metabolites in two fruit matrices. The compounds investigated belonged to different chemical families of insecticides, acaricides, fungicides, and herbicides; several metabolites were also included. Quantification was conducted using matrix-matched standards calibration; response was a linear function of concentration in the range tested (10–500 ng mL⁻¹). The method was validated with blank samples of lemon and raisin spiked at 0.01 and 0.1 mg kg⁻¹, and recoveries were satisfactory, between 70 and 110%, for most of the pesticides tested and relative standard deviations were below 15% (n = 5 at each spiking level). Excellent sensitivity resulted in limits of detection for all compounds well below 0.01 mg kg⁻¹, with the limit of quantification being validated at 0.01 mg kg⁻¹. The UPLC system generates narrow peaks (approx. 5 s), thus increasing peak height and improving sensitivity. This improved separation efficiency facilitates adequate resolution not only of the analytes but also of matrix interferences compared with conventional HPLC. The method developed could also resolve some geometric isomers. The main advantage of this approach is the high sample throughput achieved because of the short analysis time, which enables satisfactory separation of all the compounds in less than 5 min per sample.     

Purity testing of sulfonic acids of different chain length by capillary electrophoresis

Summary A CZE method has been developed for the purity testing of sulfonic acids. By use of an optimized electrolyte system, short analysis times and high resolution (R _S=2–4) can be achieved for inorganic anions and for alkyl sulfonic acids from methane-1- to decane-1-sulfonic acid. By use of indirect UV detection by-products of different sulfonic acids can be determined at the 2 m level, equivalent to 0.02%,w/w. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

The spatial distribution of poly(methyloctylsiloxane) deposited by solvent evaporation in the pores of HPLC silica particles

Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed in the pores. Measurements of the surface area (BET, N₂) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Microsequential injection analysis: Determination of rutin and quercetin in food supplements and pharmaceutical products

Conditions for the oxidative coupling of rutin and quercetin with 3-methylbenztiazolinon-2-hydrazone have been determined under the conditions of microsequential flow analysis (‘lab-on-a-valve’). To provide the high sensitivity of the determination, methods aimed at improving the overlapping of the zones in the flow have been utilized; these are stopped flow and injection of a ‘spacer’ zone. Good results have been obtained using a new approach, the injection of a ‘spacer’ zone with a rate gradient. A program of operations for the automatic spectrophotometric determination of rutin and quercetin has been composed. The analytical range is (6–50) × 10⁻⁵ M for the determination of rutin and (5–50) × 10⁻⁵ M for the determination of quercetin, the productivity of analysis being 59 samples per hour. The procedure has been applied to the analysis of plant extracts and pharmaceutical product Askorutin.     

Flow injection chemiluminescence determination of medazepam

A new flow injection chemiluminescence method for the assay of medazepam is explored. The method involves the use of permanganate in sulfuric acid for the oxidation of medazepam with the emission of chemiluminescence detected by a photomultiplier tube. A simplex procedure was employed for optimising the conditions for high sensitivity detection, which were found to be 1.03 × 10^–3 mol L^–1 permanganate, 0.153 mol L^–1 sulfuric acid and 3.43 mL min^–1 flow rate. The linear calibration range was 3.7 × 10^–5 to 1.7 × 10^–3 mol L^–1. The detection limit (3σ) and the sample throughput were 1.85 × 10^–5 mol L^–1 and 100 per hour, respectively. The relative standard deviation for 5 replicate determinations of 1.9 × 10^–4 mol L^–1 medazepam was 0.15%. Common excipients (starch, glucose, maltose, lactose) used in pharmaceutical preparations had no effect. Received: 2 February 1998 / Revised: 20 May 1998 / Accepted: 25 May 1998     

New dynamic axial compression columns with means for monitoring floating adapter position. Column design and utilisation in low pressure LC on soft packings

Summary The design of new dynamic, axial-compression columns with a system for continous packed bed adjustment and monitoring of the floating adapter position is described. The columns are meant for liquid chromatography at low pressures (up to 8 bar) in aqueous and organic media with stationary phases of all types. The columns have adapter position pickups for continuous automatic monitoring of the bed height (original “swellographic” monitoring). The column described with gas pressurisation was tested with soft Sephadex G-10 and G-25. In spite of the reduction in external porosity there was no dramatic increase in back-pressure. The column proved to provide long-term stability of the packed bed and improvement in resolution. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

New long-chained feruloyl ester from the bark of <Emphasis Type="Italic">Cedrelinga catenaeformis</Emphasis>

Tetradecyl ferulate and a new n-alkyl ester of 3-hydroxy-4-methoxy-trans-cinnamate (hexacosanylisoferulate) have been isolated from Cedrelinga catenaeformis Duke (Leguminoseae). The structures were determined by 1D- and 2D-NMR spectroscopy, mass spectrometry, chemical transformations and finally from unambiguous synthesis. This is the first report of long chained cinnamic acid ester derivative from the genus. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 214–216, May–June, 2007. Dedicated to Profs. S. El-Kousy, E. E. A. El-Khrisy, and K. B. G. Torssell on the occasion of their 60^th, 65^th, and 75^th birthdays.     

高精度四极质谱检测限测试和影响因素分析

高精度四极质谱仪(QMS)的气体分压精确测量功能与其使用方法关系密切.采用包含有四极质谱仪、真空系统和进样系统的质谱参数测试装置,针对工作及系统参数对质谱测试结果的影响开展研究.试验结果表明:无论是扫描速率、质量数分辨率、电压和探测器等质谱工作参数,还是真空本底、工作真空和气体种类等系统参数都会对质谱测试结果尤其检测限产生一定影响.试验获得了特定条件下的最优参数并进行比较.采用获得的最优参数组合,通过测量空气中极低含量稀有氪气和氙气的同位素谱图,可获得一定条件下法拉第杯(FC)、二次电子倍增器(SEM)和离子计数器(CP)等3种探测器的最小可检浓度,分别为17.3×10-9、0.34×10-9和0.15×10-9.其中SEM和CP的检测限最低,适合用于微量气体分析.     

Optimization of the electrokinetic sample introduction in capillary electrophoresis for the ultra trace determination of anions on silicon wafer surfaces

Summary A capillary electrophoretic method for the ultra trace determination of anions on silicon wafer surfaces is presented. In several sets of experiments designed according to the methodology of Taguchi, electrokinetic sample introduction with transient isotachophoretic preconcentration was simultaneously optimized for peak height, peak area, peak asymmetry, efficiency, peak resolution, and reproducibility of migration time and peak area. The blank reading of the method showed no cross contamination. Thus, a detection limit of 10 nmol L⁻¹ and a linear range from 50 to 500 nmol L⁻¹ were obtained and verified by two independent instruments. Furthermore, the method was applied to the determination of anions on wafers from a regular production line wetting the whole wafer surface with ultrapure water. The capillary electrophoretic results agree with those obtained by ion chromatography. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996.     

Diazocoupling reaction for the spectrophotometric determination of physiologically active catecholamines in bulk and pharmaceutical preparations

A simple and sensitive spectrophotometric method for the determination of four catecholamines viz., adrenaline bitartarate (ABT), methyldopa (MDP), dopamine hydrochloride (DPH), and levodopa (LDP), in both pure form and in pharmaceutical formulations is described. The method is based on the reaction of diazotized sulphanillic acid (DSA) with catecholamines in a basic medium to yield orange-red colored products having absorption maxima at 507 nm for MDP and at 475 nm for others analytes. The colored species obeyed Beer’s law in the range of 1–27, 0.5–17, 0.6–15, and 1.5–19.2 μg/mL for ABT, MDP, DPH, and LDP, respectively. The molar absorptivity values as obtained from Beer’s law data were found to be 0.812 × 10⁴, 0.947 × 10⁴, 0.927 × 10⁴, and 0.709 × 10⁴ L/(mol cm), while Sandell’s sensitivity values were observed to be 412.03, 25.15, 20.44, and 27.81 ng/cm² for ABT, MDP, DPH, and LDP, respectively. Common excipients did not interfere with the proposed method. The results of the proposed methods compare favorably with those of official methods. The proposed method offers a simplicity, reliability, rapidity, and accuracy compared to the existing methods. The text was submitted by the author in English.     

Contribution of the lipophilic buffer to chiral recognition under reversed-phase conditions

Summary A lipophilic buffered aqueous mobile phase, without organic modifier, was used for the high performance liquid chromatographic enantioseparation of D,L-lactic acid on a Merck ChiraSpher (250 mm×4 mm i.d.) column in which the chiral selector is poly(N-acryloyl-S-phenylalanine ethyl ester) bonded to a spherical silica particle. The lipophilicity of the buffer was achieved by addition of triethylammonium phosphate, the ‘ethyl’ apolar chains of which dynamically modified the ChiraSpher stationary phase and increased its hydrophobic character. The ion-paired (cethyltrimethylammonium bromide) analyte enantioseparation was realized by hydrogen-bonding and dipole-dipole complexation on the ChiraSpher stationary phase, superimposed on simultaneous reversed-phase partitioning. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Fast supercritical fluid chromatography using capillaries packed with nonporous particles

Summary Packed columns containing microparticles provide high column efficiency per unit time and strong retention characteristics compared with open tubular columns, and they are favored for fast separations. Nonporous particles eliminate the contribution of solute mass transfer resistance in the intraparticle void volume characteristic of porous particles, and they should be more suitable for fast separations. In this paper, the evaluation of nonporous silica particles of sizes ranging from 5 to 25 μm in packed capillary columns for fast supercritical fluid chromatography (SFC) using neat CO₂ is reported. These particles were first deactivated using polymethyl-hydrosiloxanes and then encapsulated with a methylphenylpolysiloxane stationary phase. The retention factors, column efficiencies, column efficiencies per unit time, separation resolution, and separation resolution per unit time for fast SFC were determined for various length capillaries packed with various sizes of polymerencapsulated nonporous particles. It was found that 15 μm nonporous particles provided the highest column efficiency per unit time and resolution per unit time for fast packed capillary SFC. Under certain conditions, separations were completed in less than 1 min. Several thermally labile silylation reagent samples were separated in times less than 5 min. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

A miniature mass analyser for in-situ elemental analysis of planetary material-performance studies

The performance of a laser ablation mass analyser designed for in-situ exploration of the chemical composition of planetary surfaces has been investigated. The instrument measures the elemental and isotopic composition of raw solid materials with high spatial resolution. The initial studies were performed on NIST standard materials using IR laser irradiance (< 1 GW cm⁻²) at which a high temporal stability of ion formation and sufficiently low sample consumption was achieved. Measurements of highly averaged spectra could be performed with typical mass resolution of m/Δm ≈ 600 in an effective dynamic range spanning seven decades. Sensitive detection of several trace elements can be achieved at the ~ ppm level and lower. The isotopic composition is usually reproduced with 1% accuracy, implying good performance of the instrument for quantitative analysis of the isotopic fractionation effects caused by natural processes. Using the IR laser, significant elemental fractionation effects were observed for light elements and elements with a high ionization potential. Several diatomic clusters of major and minor elements could also be measured, and sometimes these interfere with the detection of trace elements at the same nominal mass. The potential of the mass analyser for application to sensitive detection of elements and their isotopes in realistic samples is exemplified by measurements of minerals. The high resolution and large dynamic range of the spectra makes detection limits of ~100 ppb possible.